Polymerization catalyst system and process



United States Patent 3,274,169 POLYMERIZATION CATALYST SYSTEM AND PROCESS Robert 0. Lindblom, Pleasant Hill, Calif., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Dec. 3, 1962, Ser. No. 242,871 36 Claims. (Cl. 26093.7)

This invention relates to improved heterogeneous catalyst systems for polymerizing olefinic compounds. More specifically, it relates to an improved heterogeneous catalyst composition comprising the reaction product of at least four essential components which are an aryl (mercaptan, a lithium compound of an alkanolamine, and two additional components as described herein. This invention is also related to a process for the polymerization of olefinic compounds catalyzed by such composition.

In the solution polymerization of propylene and other olefins, it has been found that with heterogeneous catalyst systems, such as complexes :formed from TiCl, with aluminum alkyls, such as AlEt etc., TiCl plus AlEt etc., there is a substantial portion of amorphous or atactic polymer formed. These atactic polymers have a random polymer structure whereas the desired isotactic type of polymer has a stereospecific type of structure in which the side branches from the linear chain are arranged in a regular repeating type of arrangement which gives desired crystalline structure and resultant desired qualities in the polymer.

The isotactic polymer of propylene, which is a hard, tough material is desired product. This is high-melting (165 175 C.), and highly crystalline (65-75% by X- ray determination). It has been noted that as the proportion of atactic polymer in mixture with the isotactic polymer is increased the tensile yield and tensile modulus properties of the composition are adversely affected.

Regardless of the molecular Weight of the atactic type of polymer, this amorphous polymer is soluble in xylene. In contrast the isotactic polymer obtained in this type of polymerization is insoluble in xylene. The low molecular weight portion of the atactic polymer resembles grease in nature. The higher molecular weight atactic polymers resemble wax in character. Both the wax and grease types are soluble in xylene, whereas the wax portion is insoluble in an equal volume mixture of isopropanol and Xylene.

Both of these atactic materials detract from desired properties in the polymer. The grease gives a slippery, undesirable surface property to the polymer in addition to other disadvantages. While substantial amounts of the wax type can be tolerated in these polymers for certain purposes, the Food and Drug Administration has set a limit of 9% where such polymer products are to be used in contact with food, etc.

Since the most economical method of recovering the polymer from the reaction mass is to vaporize the solvent therefrom, this atactic byproduct is left in the isotactic polymer with resultant disadvantageous results on the properties.

Removal of such atactic byproduct by extraction involves extra processing steps which increase the cost of production of the desired polymer. Recovery of the desired isotactic polymer by precipitation, thereby retaining the atactic byproduct in the polymerization solvent, likewise entails additional processing steps and expense. In addition to the increased expense such methods do not give completely satisfactory results.

Therefore, the logical method for avoiding the necessity to remove substantial amounts of atactic polymer, in order to obtain the desired properties in the polymeric ice olefin, is to avoid the formation of substantial amounts of such atactic material.

A number of catalyst systems have been tried in an attempt to avoid or to reduce to a permissible amount the formation of such atactic polymers as byproducts in the production of the desired isotactic polymeric olefin. Whi'le certain catalyst systems give some small decrease in the amount of atactic byproduct, they produce side effects which are almost as disadvantageous, such as *a decrease in the yield of polymer. Certain other catalyst systems actually increase the amount of atactic material. In other words, most polymerization catalyst systems either are non-effective in reducing the amount of such byproduct formedor where there is any improvement in this respect, cerain other disadvantages result to offset such improvement.

In a copending application filed the same date herewith, Ser. No. 242,848, a new catalyst composition comprising a lithium alkanolamine is disclosed and claimed. It is also disclosed and claimed that, in the solution polymerization of olefinic compounds, the amount of the xylene-soluble polymer is reduced by the use of this new catalyst composition.

In accordance with the present invention, a new catalyst composition has been found. It has also now been found that, by the use of this catalyst composition, the proportion of atactic polymer formed in the solution polymerization of propylene, butene-l and other olefin-s which normally form substantial amounts of atactic poly mer byproduct in heterogeneous catalyst systems, can be reduced without any disadvantageous side effects to an amount which is not harmful to the properties of the desired polymer. This new catalyst composition is the reaction product obtained upon mixing an aryl mercaptan and a lithium derivative of an alkanolamine together with at least two other components C and D as described herein.

In fact, in many instances, the catalyst composition of this invention actually contributes other improvements and in the polymerization of ethylene 'where the formation of such undesirable byproducts is not such a great problem as with propylene, etc., .it is found that this aryl mercaptan-lithium alkanolamine catalyst composition is beneficial in increasing the rate of polymerization over that otherwise experienced.

The improvement effected by the aryl mercaptan and lithium alkanolamine reaction product is especially surprising in view of the fact that sulphur compounds are known to act as poisons in such heterogeneous catalyst systems particularly with TiCl -AlEt For example, 20 parts per million of carbonyl sulphide in propylene monomer reduces the polymerization rate nearly to zero. Likewise aryl mercaptans, such as thiocresol, used by themselves are quite effective poisons in a TiCl -AlEt system used in the polymerization of propylene. Thus, only a very slight reduction in atactic polymer is effected with thi-ocresol whereas the overall polymer yield is reduced to an impractically low value.

The catalyst compositions described herein, in addition to being effective in reducing the proportion of atactic polymer, also raise the molecular Weight of the product and increase the total polymer yield. In cases where it is desirable to control the molecular weight, well known means such as the use of diethyl zinc can be used to lower the molecular Weight. This particular agent has little effect 'on the yield and the isotacticity of the product.

The term aryl mercaptans, as used herein, means those mercaptans in which the sulfur of the thiol group is directly attached to an aromatic nucleus, preferably a benzene nucleus. Particularly preferred are phenyl mercaptan and alkyl derivatives thereof in which the alkyl 3 groups are attached to the aromatic nucleus. In some cases the alkyl group gives improved solubility although it is found not necessary to have more than 20 carbon atoms in an alkyl group for such purpose. The total number of carbon atoms in the aryl compound is advantageously no more than 30.

While alkyl and cycloal kyl mercaptans, substituted for the aryl mercaptans in the compositions of this invention, have some effect in reducing the amount of atactic polymer produced as byproduct in the polymerization of olelfiIlS, it is generally not more than the reduction effected by corresponding lithium alkanolamine compositions without the mercaptan. It is believed, therefore, that in such cases this reduction in atactic polymer is caused by the composition regardless of the presence of the alkyl or cycloalkyl mer-captan.

Typical of the phenyl mercaptans which are particularly preferred in the practice of this invention, are the following: phenyl mercaptan, tolyl mercaptan (thiocresol), xylyl mercaptan, ethylphenyl Inercaptan, propylphenyl mercaptan, octylphenyl mercaptan, decylphenyl mercaptan, dodecylphenyl mercaptan, eic-osylphenyl mercapt-an, etc.

Other aryl mercaptans which are useful are naphthyl mercaptan, methylnaphthyl inercaptan, amylnaphthyl mercaptan, diphenyl mercaptan, butyldiphenyl mercaptan, etc.

The lithium alkanolamines which have been found particularly useful reagents in preparing the catalyst compositions of this invention are those derived from alkanolamines having at least two hydroxy groups present in the molecule and having the nitrogen atom in the amine at least disubstituted and preferably trisubstituted. It is generally preferred to have not more than three carbon atoms separating a hydroxy group from an amino group. Advantageously, .the hydroxy and amino groups are on adjacent carbon atoms. While lithium derivatives of monoa'lkanolamines have been found to give satisfactory results, it is preferred to use lithium derivatives of dialkanolamines and advantageously trialkanolamines. It is also advantageous .to have not more than 60, preferably not more than 20 carbon atoms in such a compound.

The exact chemical structure of the resultant catalyst composition is not known. However, while applicant does not wish to be restricted to any particular structure or formula of the resultant product, it is apparent from the nature and activity of the composition that the lithium alkanolamine undergoes reaction with the other components. Moreover, in view of the reactive nature of these components, no particular reaction conditions are required to promote this reaction. Reaction occurs merely upon mixing the components under anhydrous conditions even at room temperature and at even lower temperatures. However, it is preferred to use room temperature, or ambient temperature, or whatever temperature is convenient.

In such compounds alk-oxy and acyloxy radicals can also be present as illustrated hereinafter. Apparent-1y such groups do not interfere with the desired effect.

Typical alkanolamines htat can be used for preparing such lithium derivatives include but are not restricted to the following:

H; CH 7 OH; (HO )HCHz)aN; (HO JHCHQQNH; (HO CHCHzhNCglL CH3 CH3 CH3 (HO CHzC lH) 3N; (HO CHzCH) zNH; (HO CH CH) 2NC2H5 CH3 CHa CH3 (HO 3H CH2)zNC3H7; (HO JHCHZ)zN CsHu; (HO JHCHzhNCsHrf CH3 HO lHCHzNHz; (HO CH2CH2)3N; (HO CHzCHzhNH (HO CH2CH)2NH2 (HO CH2CH2CHz)3N; (HO CHzCHzCHzhNH CH3 I (HOCHziJHhNCal-Iv; (HoornomoHmNom (HO CH2CHD2NC H11; HOCHQCHZNHZ (HOCH CH CEDMN; (HOCH CH CHQZNH (I-IOCHzCHzCHflzNCaH-r; (HOCHzCHzCHzhNCaHu HO CHzCHzCHr-NHa; HOCHzCHzCH2N(C2H5)2 CH3 HOCH2CH2CH2N(C4H9)2; HOCHCH2N(CzH5)z CH HOCHzCNHCzHs; HOOH2CH2N(CZH5)2; HOCHgCHzN(C4H0)z lHa V HOCH2CH2NHC4H9; (HOCHCHQaN; (HOCHCHzhNCzHs (ilzHa C 2Hs (HOCHCH)QN; (HOCH-CI'DzNCgli;

CH3 CH3 CH3 (ilHa CH3 (HOCHCH2CH2CH)3N; (HOCHzCH)zN; (HOCHzChNH CH3 CH3 CzHs CH3 (HO CH2CHCH2)3N; HO CHCHZN(CH2CHO CH3):

( /H3 3H3 CH3 HO CHzCH2(NHCH2CH2)aOH HO CHzCHzN(CH2CHzNHCH2CH2OH)2 (HO CHCHzMNCHzCHOCzHs; HO CHCH2N(CHZCHO C4110):

6H. 611. ()H; (in.

H0 CHCH2N(CH2CHO O C CH3):

CH CH3 (HO CHCHzhNCHzCHO O C CaHs CH3 CH3 (HOCHCH3)2NCHZCHO O CCHa HO CHCH2N(CH:CHO O C 011200135)! CH3 CH3 (HO CHCH2)zNCH2CHO O C Cal-I11 CH: CH:

etc.

Lithium alkanolamines suitable for the above purpose are new chemical compounds of the formula wherein Z is a divalent aliphatic hydrocarbon radical of no more than 30 carbon atoms and derivatives thereof in which the derivative groups are each selected from the class consisting of OR, OLi and NR groups and there are at least 2 and no more than 4 carbon atoms between said valencies, R represents a radical selected from the class of hydrogen, alkyl and acyl radicals advantageous- 1y having no more than 20, preferably no more than 8 carbon atoms therein and R represents a radical of the class consisting of hydrogen, alkyl radicals and derivatives of said alkyl radicals in which the derivative groups are each selected from the class consisting of OR, OLi and NR groups, R" represents hydrogen or an alkyl radical or a derivative of an alkyl radical in which each derivative radical is selected from the class of hydrogen, OR, OLi and NR and R' is either hydrogen or an alkyl radical, the alkyl radicals represented by R, R" and R each having no more than 20 carbon atoms, and in said compound the total number of carbon atoms being no more than 60, preferably no more than 20, the number of lithium atoms and nitrogen atoms each being no more than 3, and the number of oxygen atoms being no more than 6. For use in the catalyst systems of this invention, the compounds advantageously :have no more than 2 and preferably no more than 1 lithium atom per molecule.

Typical lithium alkanolamine compounds suitable for use in this invention include but are not restricted to the following:

CH3 CH3 CH3 OH:

(LlOCHCI'Ifl3N, LlOCHCH2N-CH2CHOH CHs CH3 CH3 (LiOGHCHzhNCzIL; LiOOI1OHZN CHZCHOCH3)2 (1H CH3 CH3 CsHu CHzCH(CH3) O C2115 LiOCHCHzNCHzCHOH; LiOCHCHz CHZCHOH CH1 CH3 CH3 CH3 LiOCH2CHN(CHC]-IzOH)2; (LiOCH2CH)2NCHCHzOH (in. 511. (1a. lHs

(LiOCHiCH)3N; (LiOCH2CH2)sN; LlOCEzCHzN CH2CH2OH)Z (LiOCHzCHz)2NCH2CH2OH; LiOCHzCHNHCHCH OH CH3 CH3 (LiOCHzCH)2NH; LiOCH2CHN(C2H5)2 CH3 CH3 LiOCHCHzN(CH2CHOC4H9)2;LiOCHCH2N(CH2CHOOCCH3):

CH3 CH3 CH3 CH3 LiOCHCI-IzNCHzCH(CH3OOCCH)a CH: CHzCHOH LiOCHCH2NCHzCH(CHa)OOCCuHs CH3 CHzCHOH LiOCHCHzNCH2CH(CHt)OOCCHzCaHs CH3 CHzCHOH C2115 LiOCH2CHl l-CHCH2OH CH CH3 LiOCHCH2NCH2CH(CHa)OOCCsHn CH3 JH2CHOH CIIa CsHn

(LiOCHzCIDzNCzHs; LiOCHzCHNCHCHzOH CH3 CH3 CH3 (LiO CHzCHhNCoHm LioCHaCHzCHzN(CH2CH2CH2OH)2 (LiOCHzCH2CH2)2NH; (LloCHzCI'I2CH2)2NH-CHZCH2CH2OH LiO CHCHzN(CH2CHO CeHs)2 CH3 CH3 L CHCHZCHZCHN(CHCH2CH2CHOH)2 CH3 CH3 CH3 CH3 LlO CH2CH2NCHZCH2N(CH2CH2OH) CHzCHzOH CHzCHzOH L10 CHzCHzNCHzCHzNCHzCHzOLi CHgCHzOH LiO CHzCHKNCI-IzCHz) 2N(CHzCHzOH)g CHgCH OH CHZCH OH LiO CH2CH2(NCH2CH2) 2NCH2CH2OLi CH2CH2OH etc.

It will be noted that some of the above compounds have alkoxy or acyloxy groups. These compounds correspond to alkauolamines having a plurality of hydroxy groups in which one or more of the hydroxy groups have been converted in part to the alkoxy or acyloxy derivatives, preferably before the lithium is attached. While it is preferred that the hydroxy groups are unsubstituted, such substitution does not interfere with the practice of this invention provided there are suflicient hydroxy groups free for the desired degree of lithium substitution or the substituted groups are easily replaced by the lithium.

In cases where compounds such as aluminum trialkyls are mixed with the lithium alkanolamines it is contemplated that aluminum may replace some of these substituent groups in forming desirable catalyst components. It is also possible to start with completely substituted alkanolamines such as the triacetate of triisopropanolamine and to introduce the lithium by reaction with lithium hydride and thereby replace one or more of the acetyl groups by lithium. In such case, the remaining acetyl groups are still susceptible to replacement by aluminum upon subsequent mixing with an aluminum trial'kyl.

The lithium alkanolam-ine compounds suitable for use in this invention can be prepared by reacting the appropriate alkanolamine with approximately the stoichiometric amount, advantageously a slight excess, of lithium hydroxide to give the desired degree of substitution, advantageously in the presence of a solvent or suspension medium capable of :forming an azeotrope with the water formed as a byproduct and thereby removing such water by refluxing and separating the water from the condensate. Such azeotrope formers are xylene, toluene, benzene, etc. The refluxing is conducted until approximately the theoretical amount of water is separated.

As described more fully hereinafter, the component C used as a reagent in preparing the catalyst composition of this invention is a compound of a metal of the periodic groups IV(b), V(b), VI(b), VIII and manganese, preferably a salt, e.g. halide, oxyhalide, etc., esters, e.g. acetylacetonate, etc., or oxide, alcoholate, etc.

Also as described more fully hereinafter, the component D used as a reagent in preparing the catalyst composition of this invention is a metal of periodic groups I, II, III, IV(b), V(b) and VI('b) or a derivative of such a metal in which each derivative group is selected \fI'OITl the class consisting of hydrogen and hydrocarbon groups.

However, a particularly suitable heterogeneous catalyst system of this invention is one using TiC1 preferably in the alpha form, as component C, and an aluminum trialkyl, such as aluminum triethyl, as component D. In such a catalyst system, it is found desirable to have an AlTi ratio of approximately 1.5-10 moles of aluminum compound per mole of Ti compound. A particularly suitable ratio is 2 moles of aluminum compound per mole of titanium compound. In this and other catalyst compositions of this invention, it is found advantageous to use 0.1-0.6 mole, preferably 0.2-0.4 mole, of lithium alkanolamine per mole of titanium compound, and 0.1-1.0 mole, preferably 0.20.8 mole of mercaptan per mole of titanium compound. The optimum ratio of mercaptan to lithium al kanolamine is 1-2 moles of mercaptan per mole of lithium compound although even a wider range of proportions can be used, for example, 0.5-3 moles of mercaptan per lithium compound have utility.

In general, the various components of the catalyst system can be added independently to the polymerization system. However, it is preferred to add the mercaptan to the aluminum trialkyl or corresponding component in the catalyst system, and then this product is reacted with the lithium alkanolamine before adding the TiCl and additional AlEt or their corresponding components.

It is also possible to react the components in the order of the mercaptan, the lithium alkanol-amine, TiCl and the Al trialkyl. Similarly, the mercaptan and the aluminum trialkyl can be pre-reacted and the lithium alkanolamine, TiCl and extra Al trialkyl reacted in that order without the pre-reaction of the lithium alkanolamine. While these are preferred orders of reaction, notable improvements are also effected when other orders of addition are used.

When the aryl mercaptan and lithium alkanolamine are omitted from the catalyst composition of this invention, approximately 12% of amorphous polymer is produced when such catalyst systems are used in the polymerization of propylene, butened, etc. However, when a catalyst composition of this invention is used in which a lithium alkanolamine and an aryl mercaptan other than a phenyl or substituted-phenyl mercaptan are reacted, the proportion of atactic polymer is reduced to approximately 7-8% of the total polymer yield. When the corresponding catalyst composition is used in which the mercaptan is phenyl mercaptan or an alkylphenyl mercaptan, then the proportion of atactic polymer is reduced to less than 6.5. Under the most favorable conditions, this proportion can be reduced to about 4% and even as low as 3.3%.

It has been found that those catalyst compositions of this invention which give increased yields very often produce such a fast polymerization rate that the temperature is more difficult to maintain. Moreover, it is found that the molecular weight of polymers made with these systems is generally higher than that obtained when other known catalyst systems are used. This is particularly true at higher polymerization temperatures. As previously stated, d-iethyl zinc can be used if desired to reduce the molecular weight. The proportion of diethyl zinc will depend on the amount of molecular weight reduction desired, generally a proportion of 0.151.5 moles of ZnEt per mole of Al trialkyl being satisfactory.

Generally the polymerizations of this invention can be conducted in a rather broad temperature range, namely, from about room temperature to about 250 C. preferably in the range of ll5150 C. However, improved effects resulting from the use of the new catalyst composition of this invention are observed at temperatures even below room temperature.

Pressures ranging from atmospheric up to 20,000 lbs. per square inch can be used, although it is generally more convenient to operate in the range of atmospheric pressure up to 500 p.s.i. depending upon the particular olefinic material used and whatever other conditions are suitable for the reaction.

In determining the amount of atactic polymer present in a particular polymerization product, it has been found that the determination is more accurate when the polymerization reaction mass is allowed to cool slowly so as to precipitate the polymer in very fine particles. The following procedure is found to be the most suitable. After the polymerization is completed, water is added to the reactor by using the pressure of the propylene (or whatever other gas is being used) in order to push the water into the reactor. The water serves to inactivate the catalyst, and then the reaction mass is allowed to cool as slowly as possible overnight. As a result, the polymer is precipitated in a fine, granular form. To this is added 200 ml. of additional xylene. The resulting mass is thoroughly slurried, and then a small portion of the xylene, about 80-90 ml. is then filtered olf. Twenty-five ml. of this filtrate is treated with 25 ml. isopropanol and allowed to stand for thirty minutes. This solution is passed through a coarse filter paper to remove precipitated wax. Twenty ml. of the filtrate is evaporated to dryness and the residue weighed. From the weight of this residue the corresponding grease fraction in the entire solution is calculated. The total xylene-soluble portion of the entire solution is determined by the evaporation of an aliquot of the original untreated xylene filtrate. The amount of wax is determined by the difference between the total xylene-soluble portion and the grease portion as calculated above. Where the respective grease and wax portions are not to be determined individually, the total xylenesoluble portion is easily determined by evaporation of an aliquot of the original untreated xylene filtrate. Both the grease and wax portions as well as the entire atactic byproduct is reduced by the improvement of this invention.

The polymerizable monomers that can be used in the practice of this invention are primarily olefins and various derivatives thereof. The derivative groups are cycloaliphatic hydrocarbon radicals, and aromatic radicals in which the aromatic nucleus can be hydrocarbon-substituted and halogen-substituted. These monomers have an ethylenic group of the formula CH =CH therein. These compounds are sometimes referred to herein as olefinic compounds. Preferably these compounds have no more than about 30 carbon atoms therein. Copolymerizations can be conducted in accordance with this process, but it is desirable that the comonomer are likewise free of polar groups other than halogen atoms attached to aromatic nuclei. Preferred comonomers are those of the same type described above.

Typical olefinic compounds that can be used in the practice of this invention include, but are not restricted to the following: ethylene, propylene, 'butene-l, n-pentene-l, 3- methyl-butene-l, 4-methyl-pentene-l, lhexene-l, octene-l, butadiene-1,3, isoprene, hexadiene-l,5, vinyl cyclohexane, vinyl cyclohexene, vinyl cyclopentane, vinyl methylcyclohexane, styrene, vinyl toluene, ethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, dimethyl styrene, di-

ethyl styrene, vinyl diphenyl, vinyl naphthalene, vinylv methylnapht-halene, ar-chloro-styrene, ar-dichloro styrene, ar-bromo styrene, ar-iodo styrene, ar-fluoro styrene, vinyl ar-chloro-naphthalene, vinyl methyl-diphenyl, vinyl archloro-diphenyl, etc.

The practice of this invention is best illustrated by the following examples. The techniques and conditions normally used in heterogeneous catalyst systems are suitable for the practice of this invention. These examples are given merely by way of illustration and are not intended to limit the scope of the invention in any way nor the manner in which the invention can be practiced. Unless specifically indicated otherwise, parts and percentages are given as parts and percentages by weight. Throughout the specification, where reference is made to polymers and polymerization, it is intended that these terms embrace copolymers and copolymerization unless otherwise indicated.

EXAMPLE I To a flask equipped with stirrer, reflux condenser, and a separator adapted to collect reflux condensate and effect the separation of a water layer therefrom, is added 200 parts of xylene, 19.1 parts of triisopropanolamine and 4.2 parts of lithium hydroxide monohydrate. This mixture is heated to and maintained at a reflux temperature for a period of approximately 2 hours, at which time substantially all of the water formed during the reaction has been separated. The monolithium derivative of triisopropanolamine which is formed has the formula CH CH This compound is separated from the xylene solvent by cooling the xylene and seeding with similar crystals. This compound sinters slightly at 177 C. and melts" at 234- 236 C. It decomposes with gas evolution and darkening at 310 C.

The corresponding disubstituted product having the formula (LiooHoHmNoHzoHoH C HQ 311 and the corresponding tri-substituted compound (LiO CHCHQQN are prepared by using 8.4 and 12.6 parts respectively of the lithium hydroxide mono'hydrate in the above procedure.

By substituting an equivalent amount of other alkanolarm'nes, such as indicated above, in place of the triisopropanolamine in the above procedures, the corresponding lithium derivatives are prepared. For example, by substituting triethanolamine, diethanolamine, diisoprop-anolamine, ethyl diisopropanolamine, diethyl isoproanolamine, ethyl diethanolamine, etc., the corresponding derivatives of this invention are prepared, namely:

LiOCH:CHzN(CHzCHzOH)z; (LiOCH2CH2)aNCHzCHzOH (LiOCH2OH2)2N; LiOCHgCHzNHCPhCHzOH; (LiOCHzCHzMNH (LiOOHCH2)2NH; LiO CHCHrNHCHzCHOH JHs CH3 CH3 (LiO OHzCH2)2N C2 a etc.

By using the appropriate alkanolamine, including the alkyl or acyl substituted derivatives, with approximately the stoichiometric amount of lithium hydroxide to give the desired degree of substitution, the various lithium .alkanolamine compounds suitable for use in this invention are prepared by the above procedure.

The procedure of Example I is the preferred method for the preparation of the lithium alkanolamine compounds of this invention starting with an al'kanolamine compound of the formula R'OZNR preferably HOZNR wherein the symbols have the meanings described above. However, other methods, such as indicated above, can also be used. Moreover, various modifications of the Example I procedure can also be used. For example in removing the water or other byproduct formed by the condensation reaction of the lithium starting compound with the alk-anolamine compound, the water, etc., can be removed from the reaction mass also by blowing an inert gas through the mass, by reducing the pressure, absorbing the water on a molecular sieve, circulating through silica gel, etc.

EXAMPLE II A small pressure reactor equipped with an inlet and a means for maintaining constant temperature is purged of atmosphere by sweeping out with oxygen-free nitrogen. Then to the reactor is added one liter of distilled, dry para-Xylene, 1 millimole of AlEt and 0.4 millimole of phenyl mercaptan. After this mixture has been allowed to react for 5 minutes, 0.4 millimole of monolithium triisopropanolamine is added and the temperature raised to and maintained for 20 minutes at 130 C. Then an additional 1.2 millimoles of AlEt and 1.6 millimoles of TiCl is added. The TiCl is of a highly crystalline alpha type of large crystallite size (+60 mesh) such as a commercially available type made by hydrogen reduction of TiCL; and designated as HTiCl The resultant product is a catalyst composition of this invention.

This catalyst composition is maintained at 126 C. and then pure dry propylene is admitted to the reactor and maintained at a pressure of 140 p.s.i.g. After 2 hours, the catalyst is deactivated by the addition of 5 milliters of water and the reaction mass is allowed to cool slowly overnight. The solid polymer precipitate is filtered from the solvent and washed with a small portion .of xylene, which wash Xylene is added to the original filtrate. By

evaporating an aliquot portion of the combined xylene filtrate and wash, the xylene-soluble portion or atactic byproduct fraction is determined.

The above procedure is repeated using no mercaptan lithium alkanolamine reagents in order to compare the elfectwhen such reagents are not used. The procedure is also repeated a number of times with variations in the type of mercaptan and temperature used. The various results are summarized in Table A:

Table A Xylenesoluble Grams of Average Mercaptan Temp., polymer Polymer per. Molec- C. in total Gram of ular polymer, T101 Weight percent None" 132 12. 6 $152 410, 000 Phenyl (Thiophenol) 126 5. 9 302 880, 000 p-Me-pl1enyl (p- Thiocres0l) 129 6.2 524 615,000 m-Me-phenyl (m- Thiocresol)- 130 1 6.3 528 480,000 o-Me-phenyl (o- 'Ihiocresol) 131 6.5 528 t 532, 000 Di-Vle-phenyl j (Thioxylenol) .130 6.3 522 525,000 4-t-Bu-phenyl 130 '6. 9 544 4 497, 000

*Also no triisopropanolamine reacted.

When the above procedure is repeated a number of times varying the mole ratio of TiAlLi-'NSH to 4-10111; 2.5-7.5-1-1-1; 1.551l1 and 48-1 1-1 respectively, similar improvements are noted in total yield of polymer and in the reduction of the percentage of atactic polymer byproduct with accompanying improvements in tensile yield and tensile modulus.

EXAMPLE III The procedure of Example II is repeated reacting the mono'lithium triisopropanol amine with varying proportions of methylphenyl mercaptan (thiocresol) in place of the phenyl mercaptan, 1 millimole of HTiCl instead of 1.6 and a temperature of 130 C., With the results shown in Table B.

Table B Millimoles Percent Total polymer Average of thiocresol xylene-soluyield per molecular ble polymer 3 gram of 'IiGl; weight;

None" 12. 6 152 410, 000

Also no triisopropanolamine is reacted.

EXAMPLE IV The procedure of Example II is repeated a number of times reacting thiocresol in each case as the mercaptan with the following components in place of the corresponding components used in preparing the catalyst in Example II and using similar amounts and mole ratio of catalyst components as used in Example II.

In each case a decrease is noted in the amount of Xylenesoluble polymer as compared to the amount produced in corresponding runs in which the thiocresol and the monolithium tri-isopropanol amine are omitted.

Improvements are likewise noted when the procedure of Example IV is repeated a number of times using catalyst compositions of this invention prepared by reacting monolithium triisopropanolamine with TiCl and TiCl respec- I 1 tively, each activated by Na, Li, K, Be, Co, Mg, Cd, Ba, Zn, Hg, Al, Ti, Zr, Hf, Th, V, Nb, Ta, Cr, Mo and W respectively.

In each case the amount of atactic polymer is reduced when a catalyst composition is used in which the mercaptan-lithium triisopropanolamine reagents are reacted as compared to polymerizations using a corresponding catalyst composition in which the mercap tan and LiTIPA are not reacted.

EXAMPLE V The procedure of Example II is repeated a number of times using independently in place of the propylene equivalent amounts of the following olefinic compounds, in each case improvements being noted in the polymerization of the olefinic compounds, the polymerization rate being increased with respect to ethylene and both polymerization rate and a decreased amount of atactic byproduct being noted with respect to the other olefinic compounds:

(a) Ethylene;

(b) Butene-l;

(c) 3-Me-butene-1;

(d) Butadiene-1,3;

(e) Isoprene;

(g) Vinyl xylene;

(h) p-Cl-styrene;

(i) Vinyl naphthalene;

(j) Vinyl diphenyl;

(k) Vinyl toluene;

(1) Vinyl cyclohexane;

(m) 5050 mole mixture of butadiene and styrene; (it) 75-25 mole mixture of propylene and styrene; n-Octene-l.

While xylene has been specified as a preferred solvent and is used throughout the preceding examples, other solvents suitable for use in heterogeneous catalyst systems for polymerization of olefinic compounds can be used. In such cases similar improvements in reduction of the amount of atactic polymer is effected even though reference is made to Xylene-soluble products. This designation is merely to identify the type of atactic polymer which it is desired to avoid in the polymerization of the olefinic compound. This is illustrated by repeating the procedure of Example I using in place of the xylene various solvents such as benzene, toluene, cyclohexane and hexane. In each case similar improvements are noted in the reduction of the atactic byproduct formed.

Other typical catalyst compositions include but are not restricted to the following in which the recited components are reacted to produce the improved catalysts of this invention:

(1) (A) A lithium alkanolamine as described herein, (B) an aryl mercaptan as defined herein, (C) the periodic group IV(b), V( b), and VI(b) metal halides of the type represented by titanium tetrachloride, zirconium trichloride, etc., and (D) an aluminum t-rialkyl, e.g. triethylaluminum, triisobutylaluminum, etc.;

(2) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a periodic group IV inorganic halide (such as titanium tetrachloride); (D) a low valence metal selected from the group consisting of alkali metals, beryllium, magnesium, zinc, cadmium, mercury, aluminum, gallium, indium, and thallium, and (D) an organic halide such as ethyl bromide.

(3) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a group IV halide, for example, titanium tetrachloride; and (D) a low valence metal such as identified in (2), for example, sodium or magnesium.

(4) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) titanium hydride; (D) an organometal compound exemplified .by aluminum alkyl halide.

(5) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) titanium dioxide; and (D) an organometal compound such as trialkylaluminum and aluminum alkyl chlorides.

(6) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a molybdenum pentachloride, and (D) an aluminum organometal compound exemplified by triethylaluminum and ethylaluminum dichlorode.

(7) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a complex metal halide exemplified by potassium fiuotitanate, and (D) an organometal compound exemplified by triethylaluminum and diethylaluminum chloride.

(8) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) an oxide of molybdenum, an alkali metal or an ammonium molybdate, and (D) triisobutylaluminum and isobutylaluminum dichloride.

(9) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a derivative of iridium, platinum and osmium selected from the groups consisting of halides, oxides and complex compounds of iridium, platinum and osmium, said complex compounds corresponding to the formula M MX wherein M is an alkali metal or an ammonium radical, M is iridium, platinum or osmium, X is a halo gen, and Y is at least 1 and the sum of x and y is equal to the valence of M, (D) a metallic organic compound exemplified 'by triethylaluminum sesquichloride.

(10) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) at least one derivative selected from the group consisting of oxides, halides, and oxyhalides of vanadium and complex salts of said halides with a member selected from the group consisting of ammonium halide and an alkali metal halide, (D) an organometal compound exemplified by triethylaluminum.

(11) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a derivative of a group VI metal selected from the group consisting of halides, oxyhalides, hydroxyhalides, oxyhydroxyhalides of a metal of the group consisting of molybdenum, tungsten, uranium, selenium, tellurium, and polonium, and complex salts of said halides and said oxyhalides with a member selected from the group consisting of halides of sodium, potassium, lithium, rubidium, cesium and ammonia, (D) an organometal compound exemplified by triethylaluminum and ethylaluminum dichloride.

(12) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a chromyl halide, and (D) at least one of the following: (a) a metal hydride or an organometal compound, (b) an organometal halide, and (c) a mixture of an organic halide and a metal, for example, chromyl chloride, ethyl bromide and magnesium.

(13) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a titanium derivative such as butyl titanate, and (D) a complex hydride such as lithium aluminum hydride (D) a halide of aluminum such as aluminum chloride.

(14) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) at least one halide of titanium, zirconium or hafnium, for example zirconium tetrachloride, and (D) at least one hydride of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum or thorium.

(15) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a member selected from the group consisting of halides of titanium, zirconium, vanadium, and molybdenum, oxyhalides of titanium, zirconium, vanadium, molybdenum and chrominum, and complex salts of said halides and oxyhalides with a member selected from the group consisting of halides of the alkali metals and ammonia, for example, titanium tetrachloride, and (D) a hydrocarbon derivative of one of the metals, zinc, cadmium, mercury and magnesium, such as diethyl zinc.

(16) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) at least one of the following: an organometal halide, a mixture of an organic halide and a metal and a complex hydride, and (D) an organo derivative of a group IV(b) metal, (E) a hydride or organo compound of a metal of groups II to VIII, inclusive.

(17) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a trior tetrahalide of titanium, zirconium,

hafnium, and germanium, (D) an organophosphorus-containing compound such as triphenyl phosphine, and (E) at least one of the following, an organometal halide, a mixture of an organic halide and a metal and a complex hydride.

(18) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a tri-tetrahalide of titanium, Zirconium, hafnium and germanium, (D) a peroxide of the formula R'OOR where R is hydrogen, alkyl, aralkyl, cycloalkyl, acyl, alkyne, or aryl, such as benzoyl peroxide, and (E) at least one of the following: an organometal halide, a mixture of an organic halide and a metal and a complex hydride, for example, ethylaluminum sesquichloride.

(19) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a trior tetrahalide of titanium, zirconium, hafnium and germanium, (D) a metal alkoxide, such as aluminum ethylate, and (E) at least one of the following: an organometal halide, a mixture of an organic halide and a metal, or a complex hydride, such as for example, ethylaluminum sesquichloride.

(20) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a halide of titanium, zirconium, hafnium, or germanium, for example, titanium tetrachloride, (D) a hydride selected from the group consisting of hydrides of aluminum, gallium, indium and thallium and complexes of said hydrides with alkali metal hydrides, lithium aluminum hydride, and (E) an organic halide such as ethyl bromide.

(21) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a halide of titanium, zirconium, hafnium, or germanium, (D) a carbide or acetylenic compound such as copper acetylide, and (E) at least one of the following: an organometal halide, a mixture of an organic halide and a free metal, and a complex hydride, such as for example, ethylaluminum sesquichloride.

(22) (A) A lithium alkanolamine, (B) an aryl mercaptan, (C) a halide of a group IV(b), V(b) or VI(b) metals, such as TiCl TiCl TiCl ZrCl etc., and (D) 7 a metal of Group IV(b), V(b) or VI(b), e.g. Ti, Zr,

Hf, V, Nb, Ta, Zr, Mo and W, or an alkyl, hydride alcoholate or ester derivative thereof, such as Ti, Zr, TiEt and Particularly preferred heterogeneous catalyst systems suitable for the practice of this invention are compositions resulting from the mixture comprising at least the four essential components, (A) a lithium alkanolamine as described herein, (B) an aryl mercaptan as described herein, (C) a compound of a metal selected from the group consisting of periodic groups IV(b), V(b), VI(b), VIII and manganese, preferably a salt, e.g. halide, oxyhalide, etc., ester, e.g. acetylacetonate, etc. or oxide or alcoholate, and (D) another of said components being selected from the class consisting of organometals, metal hydrides, and metals of periodic groups I, II, III and IV(b), V(b) and VI(b). For example, component A can be any of the various alkanolamines enumerated herein. Component B can be any of the various aryl mercaptans illustrated herein. Component C is a halide, a1- coholate, oxide or ester of Ti, Zr, Hf, Th, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, and Mn. Component D is Na, Li, K, Be, Ca, Mg, Cd, Ba, Zn, Hg, Al, Sc, Ti, Zr, Hf, Th, V, Nb, Ta, Cr, M or W, or a derivative of such a metal in which the derivative groups are each selected from the class consisting of hydrogen and hydrocarbon radicals, such as alkyl, cycloalkyl, alkenyl, cycloalkenyl and aryl radicals, the hydrocarbon portions of said radicals each having no more than 10 carbon atoms, preferably no more than 6 carbon atoms.

Typical examples of component C are: TiCl TiCl TiCl TiBr TiF TiI Ti(OC H Ti(OC H,-,)

'Ti(OCl) Cl titanium acetylacetonate, TiCl (OCI-I zirconium acetylacetonate, vanadium oxyacetylacetonate,

' NbCl TaCl CrCl chromium acetylacetonate, MoCl WCI MnC1 NiCl FeCl FeCl etc.

Typical examples of component D are: the various metals themselves and derivatives such as Al(C H Most particularly preferred are catalyst combinations of a lithium alkanolamine and an aryl mercaptan as described herein, with a titanium halide having a valency of at least 2, advantageously a chloride, e.g., TiCl TiCl TiCl etc. and an aluminum trialkyl, preferably one in which the alkyl group has no more than 6 carbon atoms Such as 2 5)2, 3)3 3 7)3, 4 9)3 etc. Particularly suitable are the a and 7 forms of titanium trichloride.

In the above catalyst systems component D is advantageously used in an amount 1.5-10 mole proportions per mole of component C, preferably approximately 2 moles of component D per mole of component C. For example, in a preferred catalyst system, 1.5-10 moles of aluminum trialkyl, preferably 2 moles, is used per mole of TiCl preferably the alpha form of the TiCl which is the form used in Example II.

The lithium alkanolamine is advantageously used in an amount of 0.05-0.77 mole preferably 0.2-0.4 mole of alkanolamine per mole of component C. For example, 0.05-0.77 mole, preferably 0.2-0.4 mole of monoli-thium triisopropanolamine, is advantageously used per mole of TiCl The aryl mercaptan is advantageously used in a proportion of 0.1-1 mole, preferably 0.2-0.8 mole, per mole of component C. For example, 0.1-1, preferably 0.2-0.8 mole of thiocresol is advantageously used per mole of TiCl The procedure of Example I is the preferred method for the preparation of the lithium alkanolamine compounds of this invention starting with an alkanolamine compound of the formula ROZNR preferably HOZNR wherein the symbols have the meanings described above. However, other methods, such as indicated above, can also be used. Moreover, various modifications of the Example I procedure can also be used. For example in removing the Water or other byproduct formed by the condensation reaction of the lithium starting compound with the alkanolamine compound, the water, etc., can be removed from the reaction mass also by blowing an inert gas through the mass, by reducing the pressure, absorbing the water on a molecular sieve, circulating through silica gel, etc.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention to the exact details shown above except insofar as they are defined in the following claims.

The invention claimed is:

1. A composition suitable for use as a polymerization catalyst comprising the product obtained upon mixing under anhydrous conditions:

(A) A lithium derivative of an alkanolamine of no more than 60 carbon atoms having the formula LiOZNR wherein Z is a divalent radical selected from the class consisting of divalent aliphatic hydrocarbon radicals of no more than 30 carbon atoms and derivatives thereof in which the derivative groups are each selected from the class consisting of OR, OLi and NR groups (said divalent radical having at least 2 and no more than 4 carbon atoms between said valencies; R represents a radical selected from the class of hydrogen, alkyl and acyl radicals having no more than 20 carbon atoms therein; R represents a radical of the class consisting of hydrogen, alkyl radicals and derivatives of said alkyl radicals in which the derivative radicals are each selected from the class consisting of OR, OLi, and NR radicals; R" represents a radical selected from the class consisting of hydrogen, alkyl radicals and derivatives of alkyl radicals in which the derivative radicals are each selected from the class consisting of OR, OLi and NR radicals; and R' represents a radical from the class consisting of hydrogen and alkyl radicals; said alkyl radicals represented by R, R" and R each having no more than carbon atoms therein, in said compound the total number of carbon atoms being no more than 60, the number of lithium atoms and nitrogen atoms each being no more than 3, and the number of oxygen atoms being no more than (B) An aryl mercaptan;

(C) A compound selected from the class consisting of halides, oxides, alcoholates and esters of metals of the periodic groups IV(b), V(b), VI(b), VIII and manganese; and

(D) A component selected from the class consisting of metals of periodic groups I, II, III, IV(b), V(b) and VI(b) and derivatives thereof in which each derivative group is selected from the class consisting of hydrogen and hydrocarbon radicals.

2. A composition of claim 1, in which said aryl mercaptan is selected from the class consisting of phenyl mercaptan and alkylphenyl mercaptans in which said alkyl groups have no more than 20 carbon atoms therein.

3. A composition of claim 2, in which said lithium compound is monolithium triisopropanolamine.

4. A composition of claim 2, in which said lithium compound is monolithium triethanolamine.

5. A composition of claim \2, in which said lithium compound is dilithium triisopropanolamine.

6. A composition of claim 2, in which said lithium compound is monolithium diisopropanolamine.

7. A composition of claim 2, in which said lithium compound is monolithium ethyl-diisopropanolamine.

8. A composition of claim 2, in which said component C is a titanium chloride in which the titanium has a valency of at least 2, and said component D an aluminum trialkyl in which said alkyl radicals have no more than 6 carbon atoms.

9. A composition of claim 8, in which said titanium chloride is TiCl 10. A composition of claim 9, in which said aluminum trialkyl is used in a proportion of 15-10 moles per mole of TiCl and said lithium alkanolamine is used in the proportion of 0.05-0.77 mole per mole of TiCl 11. A composition of claim 10, in which said lithium alkanolamine is monolithium triisopropanolamine.

12. A composition of claim 11, in which said monolithium triisopropanolamine is used in the proportion of 0.2-0.4 mole per mole of TiCl 1 3. A composition of claim 12, in which said aryl mercaptan is thiocresol.

14. A composition of claim 12, in which said aryl mercaptan is phenyl mercaptan.

15. A composition of claim 1, in which said aryl mercaptan is thiocresol.

'16. A composition of claim 1, in which said aryl rnercaptan is phenyl mercaptan.

17. A polymerization process comprising the step of polymerizing an olefinic compound having no more than 30 carbon atoms therein selected from the class consisting of olefins having a OH '=OH group and derivatives thereof in which each derivative group is selected from the class consisting of cycloalkyl, aryl and haloaryl groups,

in which haloaryl groups each halogen atom is attached 1 directly to the aromatic nucleus of the aryl group, at a (A) A lithium derivative of an alkanolamine of no more than 60 carbon atoms having the formula LiOZNR wherein Z is a divalent radical selected from the class consisting of OR, OLi, and NR radicals, said divalent radical having at least 2 and no more than 4 carbon atoms between said valencies; R' represents a radical selected from the class consisting of hydrogen, alkyl and acyl radicals having no more than 20 carbon atoms therein; R represents a radical of the class consisting of hydrogen, alkyl radicals and derivatives of alkyl radicals in which the derivative radicals are each selected from the class consisting of OR, OLi and NR radicals; R" represents a radical selected from the class consisting of hydrogen, alkyl radicals and derivatives of alkyl radicals in which the derivative radicals are each selected from the class consisting of OR, O Li and RN radicals; and R' represents a radical selected from the class consisting of hydrogen and alkyl radicals; said alkyl radicals represented by R, R" and R" each having no more than 20 carbon atoms therein, the total number of carbon atoms in said compound being no more than 60, the number of lithium atoms and nitrogen atoms each being no more than 3, and the number of oxygen atoms being no more than 6;

(B) An aryl mercaptan,

(-C) A compound selected from the class consisting of halides, oxides, alcoholates and esters of metals of the periodic groups IV(b), V(b), VI(b), VIII and manganese, and

(D) A component selected from the class consisting of metals of periodic groups I, II, III, IV(b), V(b) and VI( b) and derivatives thereof in which each derivature group is selected from the class consisting of hydrogen and hydrocarbon radicals.

18. The process of claim 17, in which said lithium compound is monolithium triisopropanolamine.

19. The process of claim 18, in which said lithium compound is monolithium triisopropanolamine.

20. The process of claim 18, in which said lithium compound is monolithium triethanolamine.

21. The process of claim 18, in which said lithium compound is dilithium triisopropanolamine.

22. The process of claim 18, in which said lithium compound is monolithium diisopropanolamine.

23. The process of claim 18, in which said lithium compound is monolithium ethyl-diisopropanolamine.

24. The process of claim 18, in which said temperature is 150 C., and said pressure is in the range of atmospheric pressure to 500 pounds per square inch.

25. The process of claim 24, in which said catalyst comprises a titanium chloride in which the titanium has a valency of at least 2, and an aluminum trialkyl in which said alkyl radicals have no more than 6 carbon atoms.

26. The process of claim 25, in which said titanium chloride is TiCl 27. The process of claim 26, in which said aluminum trialkyl is present in a proportion of 1.510 moles per mole of TiCl and said lithium alkanolamine is present in the proportion of ODS-0.77 moles per mole of T iC1 28. The process of claim 27, in which said lithium alkanolamine is monolithium triisopropanolamine.

29. The process of claim 27, in which said monolithium triisopropanolamine is present in the proportion of 0.2-0.4 mole per mole of TiCl 30. The process of claim 29, in which said olefinic compound is propylene.

31. The process of claim 30, in which said aryl mercaptan is thiocresol.

32. The process of claim 30, in which said aryl mercaptan is phenyl mercaptan.

33. The process of claim 17, in which said olefinic compound is propylene, said component C is TiCl and 17 said component D is an aluminum trialkyl in which said alkyl groups each have no more than 6 carbon atoms.

34. The process of claim 17, in which said temperature is 115-150 C., and said pressure is in the range of atmospheric pressure to 500 pounds per square inch.

35. The process of claim 34, in which said aryl mercaptan is thiocresol.

36. The process of claim 34, in which said aryl mercaptan is phenyl mercaptan.

References Cited by the Examiner UNITED STATES PATENTS 2,996,459 8/1961 Andersen 260-949 JOSEPH L. SCHOFER, Primary Examiner.

F. L. DENSON, Assistant Examiner. 

17. A POLYMERIZATION PROCESS COMPRISING THE STEP OF POLYMERIZATION AN OLEFINIC COMPOUND HAVING NO MORE THAN 30 CARBON ATOMS THEREIN SELECTED FROM THE CLASS CONSISTING OF OLEFINS HAVING A CH2=CH-GROUP AND DERIVATIVES THEREOF IN WHICH EACH DERIVATIVE GROUP IS SELECTED FROM THE CLASS CONSISTING OF CYCLOAKLY, ARYL AND HALOARYL GROUPS, IN WHICH HALOARYL GROUPS EACH HALOGEN ATOM IS ATTACHED DIRECTLY TO THE AROMATIC NUCLEUS OF THE ARYL GROUP, AT A TEMPERATURE OF ROOM TEMPERATURE TO 250*C., AT A PRESSURE OF ATMOSPHERIC PRESSURE TO 20,000 POUNDS PER SQUARE INCH, IN THE PRESENCE OF A CATALYST COMPOSITION COMPRISING THE REACTION PRODUCT OBTAINED UPON MIXING THE FOLLOWIN FOUR COMPONENTS: (A) A LITHIUM DERIVATIVE OF AN ALKANOLAMINE OF NO MORE THAN 60 CARBON ATOMS HAVING THE FORMULA LIOZNR, WHEREIN Z IS A DIVALENT RADICAL SELECTED FROM THE CLASS CONSISTING OF OR'', OLI, AND NR2" RADICALS, SAID DIVALENT RADICAL HAVING AT LEAST 2 AND NO MORE THAN 4 CARBON ATOMS BETWEEN SAID VALENCIES; R'' REPRESENTS A RADICAL SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, ALKYL AND ACYL RADICALS HAVING NO MORE THAN 20 CARBON ATOMS THEREIN; R REPRESENTS A RADICAL OF THE CLASS CONSISTING OF HYDROGEN, ALKYL RADICALS AND DERIVATIVES OF ALKYL RADICALS IN WHICH THE DERIVATIVE RADICALS, ARE EACH SELECTED FROM THE CLASS CONSISTING OF OR'' OLI AND NR2" RADICALS; R" REPRESENTS A RADICALS SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, ALKYL RADICALS AND DERIVATIVES OF AKYL RADICALS IN WHICH THE DERIVATIVE RADICALS ARE EACH SELECTED FROM THE CLASS CONSISTING OF OR'', OLI AND RN2'''''' RADICALS; AND R'''''' REPRESENTS A RADICAL SELECTED FROM THE CLASS CONSISTING OF HYDROGEN AND ALKYL RADICALS; AD LKYL RADICALS REPRESENTED BY R, R" AND R" EACH HAVING NO MORE THAN 20 CARBON ATOMS THEREIN, THE TOTAL NUMBER OF CARBON ATOMS IN SAID COMPOUND BEING NO MORE THAN 60, THE NUMBER OF LITHIUM ATOMS AND NITROGEN ATOMS EACH BEING NO MORE THAN 3, AND THE NUMBER OF OXYGEN ATOMS BEING NO MORE THAN 6; (B) AN ARYL MERCAPTAN, (C) A COMPOUND SELECTED FROM THE CLASS CONSISTING OF HALIDES, OXIDES, ALCOHOLATES AND ESTERS OF METALS OF THE PERIODIC GROUPS IV(B), V(B), VI(B), VIII AND MAGANESE, AND (D) A COMPONENT SELECTED FROM THE CLASS CONSISTING OF METALS OF PERIODIC GROUPS, I, II, III, IV(B), V(B) AND VI(B) AND DERIVATIVES THEREOF IN WHICH EACH DERIVATURE GROUP IS SELECTED FROM THE CLASS CONSISTING OF HYDROGEN AND HYDROCARBON RADICALS. 